Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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AN ELECTRODE MATERIAL AND COMPONENTS THEREFROM FOR USE IN AN
ELECTROCHEMICAL DEVICE AND PROCESSES FOR THE MANUFACTURE
THEREOF
FIELD OF INVENTION
The present invention relates to materials, components and manufacturing
techniques thereof for
use in electrochemical devices, such as electrochemical cells. In particular,
the present invention
relates to dry blends or pastes for use in and/or for the manufacture of an
article used in an
electrochemical device, an article, such as an anode or a cathode, used in an
electrochemical
device, comprising a dry film comprising said dry blend and/or derived from
said dry blend, paste
or pasty film, a method for manufacturing said article, an electrochemical
device, comprising
said dry blend and/or made from said dry blend, paste, dry film and/or pasty
film, said article
and/or an article made according to said method and an apparatus for the
manufacturing of said
materials and articles.
BACKGROUND
Traditional electrodes for electrochemical devices, such as batteries and
supercapacitors, are
made by slurry coating processes in which the electrode ingredients, including
any glue like
binders or other additives, are mixed into a slurry, which is then formed at
high temperatures by
spreading the slurry on a thin sheet of substrate foil and dried in an oven.
The process is
expensive, energy intensive, time consuming, and due to the large amounts of
process additives,
such as toxic solvents, is damaging to health and the environment. A new blend
of electrode
materials eliminating or greatly reducing the need for process additives, and
in particular,
removing or greatly reducing the need for solvents, and a process to produce
electrodes for
electrochemical devices eliminating the cost and complexity or removing and
handling such
process additives would be beneficial to both commerce and industry.
SUMMARY OF INVENTION
Described is a process mixture for use in and/or for the manufacture of one or
more dry films.
The dry films can be incorporated in an article. The article can be
incorporated in an
electrochemical device. The process mixture ingredients may comprise one or
more reactive
materials and/or reactive composites. The the reactive composite may comprise
one or more
reactive materials and one or more matrix materials. The reactive composite
alone, and/or the
process mixture, with or without the reactive composite, may comprise one or
more binders. The
ratio of ingredients, in the process mixture as a whole and/or in the reactive
matrix, may be
predetermined ratio. The process mixture may a dry blend or a paste. The
process mixture may
further comprise one or more conductive additives. The conductive additives
may be in a
predetermined ratio to the other ingredients of the process mixture. One or
more of the binders
may be an element of the process mixture as a whole. One or more of the
binders may be an
element of one or more of the reactive composites. One or more of the reactive
materials may be
an active material and/or a precursor material. The precursor material may be
a precursor to an
active material. One or more of the reactive composites may be an active
composite and/or a
precursor composite. One or more of the precursor materials may be a precursor
to an active
material. Some or all of the reactive materials and/or some or all of the
reactive composites and/or
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some or all of the matrix materials and/or some or all of the binders and/or
some or all of the
conductive additives and/or any combination thereof in the process mixture
and/or reactive
composite may be in the form of particles and/or grains and/or are in solid
phase. At least some
of the one or more binders may be fibrillizable and/or is fibrillized. The
process mixture may
comprise substantially no non-fibrillizable binders. The paste may comprise
less than 85% liquid
and/or background fluid by mass. The dry blend and/or a dry blend derived from
the paste may
comprise substantially no liquids. The dry blend and/or a dry blend derived
from the paste may
comprise a dry powder. The reactive materials may be dry reactive materials.
The reactive
composites may be dry reactive composites. The matrix materials may be dry
matrix materials.
The binders may be dry binders. The conductive additives may be dry conductive
additives. The
dry blend may be made from a paste. The dry blend may comprise substantially
no processing
additives or other intentionally added material. The conductive additives of
the process mixture
may comprise carbon or an allotrope thereof and/or a metal. The conductive
additive may be in
the form of a conductive high aspect ratio particle. One or more of the
reactive materials may
comprise a salt comprising a metal containing cation and an anion. One or more
of the matrix
materials comprises carbon and/or an allotrope of carbon. The metal of the
salt's metal containing
cation may comprise an alkali metal and/or the salt's anion is a halide. The
salt's alkali metal
may comprise Li, Na and/or K. The salt's halide may comprise F, Cl, S and/or
Br.
An article for use in an electrochemical device is described, the article may
comprise a dry film.
The dry film may comprise a dry blend according the invention and/or be
derived from a process
mixture according to the invention. The dry film may be a freestanding film
and/or a supported
film. The dry film may be continuous and/or adhesive. Some or all of the one
or more conductive
additives in the film may makes direct ohmic contact within the dry film. The
one or more
conductive additives may form one or more conductive pathways within the dry
film. The dry
film may be an element of an anode and/or a cathode. The dry film may be
bonded to, adhered
to or otherwise coupled with a substrate, such as a final substrate. The final
substrate may be an
adhesive substrate. The final substrate may be electrically conductive. The
final substrate may
have an adhesion enhancing surface and/or an adhesion enhancing morphology.
The adhesion
enhancing surface may be a rough and/or porous and/or textured surface. The
electrically
conductive final substrate may be a current collector. The current collector
may be an anodic
current collector or a cathodic current collector. The dry film may be bonded
to, adhered to or
otherwise coupled with the anodic current collector or the cathodic current
collector. The dry
film bonded to, adhered to or otherwise coupled with the anodic current
collector may be an
anode. The dry film bonded to, adhered to or otherwise coupled with the
cathodic current
collector may be a cathode. Some or all of the reactive material and/or
reactive composite, matrix
material and binder may be intermixed within the dry film with a first ratio,
wherein some of the
reactive material and/or reactive composite, matrix material and/or binder is
intermixed within
the dry film with at least one opposing different second ratio, wherein the
dry film with first ratio
of materials provides enhanced electrode functionality, and wherein the dry
film with the second
ratio of materials provides enhanced adhesive functionality. Some or all of
the conductive
additive may be intermixed within the dry film with a first ratio, wherein
some of the conductive
additive may be intermixed within the dry film with at least one opposing
different second ratio,
wherein the dry film with the second ratio may provide higher conductivity
than the dry film with
the first ratio. The ratio of reactive material and/or reactive composite
and/or matrix material
and/or binder and/or the conductive additive may be distributed within the dry
film with a
gradually changing gradient of one or more of the reactive materials and/or
reactive composites
and/or matrix materials and/or binders and/or conductive additive.
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A method for making a dry film or an article for an electrochemical device, is
described. The
method may comprise the steps of preparing a process mixture according to the
invention by
mixing the predetermined ratio of ingredients present in process mixture in a
mixer and then
fottiting the process mixture into the film of an article of the invention in
a film former, wherein
the film is a dry film or pasty film. One or more of the reactive composites,
may be produced by
separately mixing one or more matrix materials and one or more reactive
materials in a mixer to
form a dry reactive composite. One or more of the reactive composites, may be
produced by
separately mixing one or more matrix materials, one or more reactive materials
and one or more
background fluids and/or dispersants in a mixer to form a wet reactive
composite. Some or all of
the mixing may be carried out by shaking, milling, grinding, shearing,
sonicating, shaking,
vibrating, mortaring, tumbling, fluidizing and/or stirring. Some or all of the
mixing may be
carried out by dispersing one or more of the matrix materials and one or more
reactive materials
and/or one or more binders and/or conductive additives in one or more
dispersants to create a
dispersion and then fully removing the dispersant to create a mixed powder or
partially removing
the dispersant to create a paste, wherein the remaining dispersant may act as
a background fluid.
Some or all of the mixing may be carried out by substantially in the absence
of any dispersant to
create a mixed powder. Some or all of the mixing may be carried out with the
additional step of
adding a background fluid to create a paste. The dispersant may be a solvent,
a suspendant, and/or
a colloidant. The dispersion may be a solution, a suspension and/or a colloid.
Dispersing may
comprise suspending, dissolving and/or colloiding. Some or all of the
dispersant may be removed
by evaporation, drum drying, filtration, chemical reaction, precipitation,
crystallization,
extraction, compression, acceleration, deceleration, centrifugation, impaction
and/or
solidification. The process mixture may be sheared during the mixing. The
evaporation may be
carried out by vibration, sonification, heating, vacuuming, spray drying,
freeze drying, fluidized
bed drying, supercritical drying and/or depressurization. The heating may be
convective,
conductive, vibrational, frictional and/or radiative heating. The method may
further comprise the
step of applying the film to a final substrate. The film may be applied to the
final substrate by
mechanical compression. The film may be sheared during film forming and/or
film application.
The final substrate may be an adhesive substrate. The mechanical compression
and/or the
shearing may be carried out by calendering between two or more calendering
cylinders having
the same or different surface speeds at the nip between the calendering
cylinders. The mechanical
compression and/or shearing can be carried out by pressing between two or more
stationary, co-
moving or non-co-moving planar or contoured plates. Some or all of the process
mixture, the
film and/or any of the components thereof may be heated and/or cooled before,
during and/or
after applying the film to the final substrate. The shearing during mixing,
film formation and or
film application may fully or partially fibrillizes some or all of the one or
more fibrillizable
binders.
An electrochemical device is described. The electrochemical device may
comprise any of the
reactive materials and/or active materials and/or precursor materials and/or
matrix materials,
and/or binders and/or current collectors, and or separators, and or anodes
and/or cathodes and or
electrolytes described in any of the various embodiments of the invention. The
electrochemical
device may comprise the process mixture of any embodiment of the invention.
The
electrochemical device may comprise the article of any embodiment of the
invention. The
electrochemical device may comprise the article made according to the method
of any
embodiment of the invention. The electrochemical device may be an
electrochemical cell. The
electrochemical cell may comprise an electrolyte and an anode and/or a
cathode. The anode may
comprise an article of the invention. The cathode may comprise an article of
the invention. The
electrochemical cell may further comprise a separator. The electrochemical
cell may be a battery
cell, a supercapacitor cell or an electrodeposition cell. The dry blend and/or
the dry film of one
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or more of the one or more articles of the electrochemical cell may be bonded
to, adhered to or
otherwise coupled with the separator. The bonding to the separator may be dry
bonding.
An apparatus for the manufacture of all or part of the described process
mixture and the described
article for use in an electrochemical device is described as well as an
apparatus for carrying out
the method. The apparatus may include means for mixing, shearing, film forming
and/or film
applying.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure la: A dry blend according to one embodiment of the invention comprising
a binder
distributed around particles of reactive material, reactive composite
comprising reactive material
and matrix material and conductive additive.
Figure lb: A dry blend according to one embodiment of the invention comprising
particles of
binder, reactive material, reactive composite comprising reactive material and
matrix material
and conductive additive.
Figure lc: A paste according to one embodiment of the invention comprising
particles of binder,
reactive material, reactive composite comprising reactive material and matrix
material and
conductive additive in a background fluid.
Figure id: A paste according to one embodiment of the invention comprising
particles of binder,
reactive material, reactive composite comprising reactive material and matrix
material and
conductive additive in a background fluid.
Figure 2a: An article according to one embodiment of the invention comprising
a dry blend
comprising a binder distributed around particles of reactive material,
reactive composite
comprising reactive material and matrix material and conductive additive
formed into a film
adhered to a substrate having a adhesion enhancing surface and morphology.
Figure 2b: A dry film according to one embodiment of the invention having two
compositions.
Figure 2c: A dry film according to one embodiment of the invention having a
continuous
variation in composition.
Figure 2d: A film in an intermediate state according to one embodiment of the
invention, wherein
the film is a pasty film and the background fluid of the paste is removed to
form a dry film.
Figure 2e: A pasty film according to one embodiment of the invention having
two compositions.
Figure 2f: A pasty film according to one embodiment of the invention having a
continuous
variation in composition.
Figure 3a: A mixing procedure for preparing a dry blend according to one
embodiment of the
invention, wherein the dry blend comprises one or more reactive materials
and/or one or more
reactive composites and one or more binders.
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Figure 3b: A mixing procedure for preparing a dry blend according to one
embodiment of the
invention, wherein the dry blend comprises one or more reactive materials
and/or one or more
reactive composites, one or more binders and one or more conductive additives.
Figure 3c: A mixing procedure for preparing a dry blend or paste according to
one embodiment
of the invention, wherein the dry blend or paste comprises one or more
reactive materials and/or
one or more reactive composites, one or more binders and one or more
conductive additives and
all or part of the one or more dispersants and/or background fluids are fully
or partially removed.
Figure 4a: An embodiment of the invention for producing a freestanding film
from a process
mixture by means of a film former calender together with an embodiment for an
article of the
invention wherein the film is deposited on a substrate by means of a separate
film applier
calender.
Figure 4b: An embodiment of the invention for producing a supported film from
a process
mixture by means of a film former calender together with an embodiment for an
article of the
invention wherein the film is deposited on a substrate by means of a combined
film applier
calender.
Figure 4c: An embodiment of the invention for producing a supported film from
a process
mixture by means of a film former calender together with an embodiment for an
article of the
invention wherein the film is deposited in a substrate by means of a combined
film applier
calender.
Figure 4d: An embodiment of the invention for producing multiple supported
films from multiple
process mixtures by means of a multiple film former calender together with an
embodiment for
an article of the invention wherein the film is deposited on a substrate by
means of a combined
film applier calender.
Figure 4e: An embodiment of the invention for producing a supported film from
a process
mixture by means of a single combined film former calender and film applier
calender.
Figure 4f: An embodiment of the invention for producing a multiple supported
films from
multiple process mixtures by means of a single combined film former calender
and film applier
calender.
Figure 4g: An embodiment of the invention for producing a supported film
having multiple layers
from a multiple process mixtures by means of multiple combined film former
calender and film
applier calenders.
Figure 5a: An embodiment of an electrochemical device according to one
embodiment of the
invention having an electrode comprising a current collector and an electrode
film and an
electrolyte.
Figure 5b: An embodiment of an electrochemical cell according to one
embodiment of the
invention having an anode comprising an anodic current collector and an anode
film, an cathode
comprising an cathodic current collector and a cathode film and an
electrolyte.
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Figure Sc: An embodiment of an electrochemical cell according to one
embodiment of the
invention having an anode comprising an anodic current collector and an anode
film, an cathode
comprising an cathodic current collector and a cathode film, an electrolyte
and a spacer.
Figure 5d: A double sided electrode having a film deposited on both side of
the same current
collector.
Figure 6a: An embodiment of mixing and film processing for freestanding film
according to one
embodiment of the invention.
Figure 6b: An embodiment of mixing and film processing for freestanding film
according to one
embodiment of the invention.
Figure 6c: An embodiment of mixing and film processing for supported film
according to one
embodiment of the invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Detailed embodiments of the present invention are disclosed herein with
reference to the
accompanying drawings.
Definitions:
"Dry" here may mean being substantially liquid-free, background fluid-free
and/or dispersant-
free, preferably less than 5% and more preferably less than 2% and more
preferably less than 1%
and more preferably less than 0.5% and more preferably less than 0.2% and more
preferably less
than 0.1% and more preferably less than 0.05% and more preferably less than
0.02% and most
preferably less than 0.01% by weight of liquid and/or dispersant.
A "liquid" here may refer to any nearly incompressible substance, such as a
fluid, that may
conform to the shape of its container but may retain a nearly constant volume
and/or density
independent of pressure, i.e., it may have a definite volume but no fixed
shape. Liquids here may
include, for instance, ionic liquids, plasmas or gels.
A "dry blend" here may refer to a mixture of solids which is, substantially
liquid and/or
dispersant-free. A dry blend may be converted to, or derived from, a paste, a
wet mixture or a
wet dispersion. The conversion or derivation may be by, for instance, drying
or reacting. The
drying or reacting may be by, for instance, evaporating, chemically reacting,
solidifying,
centrifuging or otherwise removing or converting to gas or solid some or all
of the liquids,
background-fluids and/or dispersants present in the paste, wet mixture, wet
dispersion or other
precursor to the dry blend.
An "electrochemical device" here many mean, for instance, an electrochemical
cell, for instance,
a battery or supercapacitor, an electrodeposition device or any other device
wherein an
electrochemical reaction takes place.
An "Electrochemical cell" here may mean a device capable of either generating
electrical energy
from chemical reactions or facilitating chemical reactions through the
introduction of electrical
energy. An electrochemical cell may comprise and anode, a cathode and an
electrolyte. The
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electrolyte may be between the anode and the cathode. An electrochemical cell
may further
comprise a separator between the anode and cathode. An electrochemical cell
may further
comprise a housing. The anode and/or the cathode may comprise a current
collector. Examples
of electrochemical cells include, but are not limited to, batteries and
supercapacitors.
"Substantially liquid and/or dispersant-free" here means having substantially
no or very low
liquid and/or dispersant, preferably having less than 5% and more preferably
less than 2% and
more preferably less than 1% and more preferably less than 0.5% and more
preferably less than
0.2% and more preferably less than 0.1% and more preferably less than 0.05%
and more
preferably less than 0.02% and most preferably less than 0.01% by weight of
liquid, background
fluid and/or dispersant.
A "Wet mixture" here may include any mixture of material that is not dry
and/or is not liquid-,
background fluid- and/or dispersant-free. Wet mixtures include wet dispersions
and pastes.
A "Wet dispersion" here may include, but is not limited to solutions,
suspensions and colloids.
Other wet dispersions are possible according to the invention. Wetting may be
by any appropriate
liquid, including, for instance, traditional liquids, ionic liquids, or gels.
Dispersing here may mean
mixing a solid with a wet dispersant to create a wet dispersion. The process
of creating a wet
dispersion is here termed wet dispersing. Here a dispersant may be a liquid,
including a traditional
liquid, an ionic liquid, or a gel, which may include a solvent, a colloid's
external phase, a
suspension's continuous phase or the like. Here, a suspendant is a dispersant
for a suspension, a
colloid continuous phase (here termed a colloidant) is a dispersant for a
colloid and a solvent is
a dispersant for a solution.
A "solution" may describe a wet dispersion, preferably an essentially
homogeneous mixture,
which may be composed of two or more substances. In such a wet dispersion, a
solute may be a
substance dissolved in another substance, termed a solvent. The solution may,
more or less, take
on some or all of the characteristics of the solvent, including, for instance,
its phase. The solvent
may be the major fraction of the wet dispersion. The process of creating a
solution is here termed
dissolving. Colloids and suspensions may be different from solutions, in which
the dissolved
substance (solute) does not exist as a solid, and solvent and solute are
essentially homogeneously
mixed.
A "suspension" may describe a wet dispersion comprising solid particles and/or
grains (an
internal phase) and a fluid (an external phase). A suspension may comprise
solid particles and/or
grains that are sufficiently large for sedimentation. The solid particles
and/or grains preferably
may be larger than 0.1 micrometer and more preferably may be larger than 1
micrometer. The
solid particles and/or grains may be larger than 10 micrometers. The solid
particles and/or grains
may be larger than 100 micrometers. The internal phase (solid) may be
dispersed throughout the
external phase (fluid) my any means. The fluid may be any appropriate fluid,
including a liquid.
Liquids here may include, in addition to traditional liquids, ionic liquids
and gels. Preferably the
internal and external phases are dispersed through mixing. The dispersion may
be aided by the
use of certain excipients and/or suspending agents. If left undisturbed for a
sufficient period, solid
particles and/or grains may eventually settle out of the suspension over time.
The process of
creating a suspension is here termed suspending.
A "colloid" may describe a wet dispersion in which one substance of insoluble
particles and/or
grains is dispersed throughout another substance. Unlike a solution, whose
solute and solvent
constitute only one phase, a colloid may have a dispersed phase (the suspended
particles and/or
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grains) and a continuous phase (the medium of suspension). In a colloid, the
mixture may be one
that does not settle over time or would take a very long time to settle
appreciably. The process of
creating a colloid is here termed colloiding.
Here "mixing" may be by mechanical or any other means, including but not
limited to agitation,
shaking, milling (e.g. ball milling), grinding, shearing, sonicating, shaking,
vibrating, mortaring,
tumbling, fluidizing and/or stirring. Other means of mixing are possible
according to the
invention.
Here a "Process mixture" here may mean a dry blend and/or a paste according to
the invention,
which may be formed into a film according to the invention, which may be a dry
film and/or a
pasty film. The process mixture may comprise, at least, a reactive material, a
matrix material and
a binder. The process mixture may further comprise a conductive additive
and/or a background
fluid.
Here a "precursor mixture" here may mean a mixture of ingredients of a process
mixture, plus
any processing additives that may be fully or partially removed in the
preparation of the process
mixture, before said process mixture is formed into a film (11) according to
the invention.
A process mixture may be prepared in a single stage or in multiple stages. If
prepared in a single
stage, all the ingredients of the process mixture may be added to the mixer at
the same time and
the ingredients may be mixed for the same time period. If prepared in two
stages, a first part of
the ingredients of the process mixture may be added to the mixer at a first
time and the first part
of the ingredients of the process mixture may be mixed for a first time period
in stage 1 and, after
the first time period has elapsed, a second part of the ingredients of the
process mixture may be
added to the mixer at a second time and the first and second parts of the
ingredients of the process
mixture may be mixed for a second time period in stage 2. If prepared in three
stages, a first part
of the ingredients of the process mixture may be added to the mixer at a first
time and the first
part of the ingredients of the process mixture may be mixed for a first time
period in stage 1 and,
after the first time period has elapsed, a second part of the ingredients of
the process mixture may
be added to the mixer at a second time and the first and second parts of the
ingredients of the
process mixture may be mixed for a second time period in stage 2 and, after
the second time
period has elapsed, a third part of the ingredients of the process mixture may
be added to the
mixer at a third time and the first, second and third parts of the ingredients
of the process mixture
may be mixed for a third time period in stage 3. Similarly, the process can
have four or more
preparation stages. In certain cases, a part of the process mixture may be
removed within or
between stages. For example, a background fluid and/or processing additive may
be added and/or
removed within or between stages. This may be, for instance to maintain
certain properties of the
process mixture within or between stages or to change certain properties
within or between
stages. Such properties may be, for instance, the viscosity, the adhesivity
and/or the background
fluid and/or processing additive concentration within the process mixture.
Some or all of the
background fluid and/or processing additive may be fully or partially removed
by any means,
including, but not limited to evaporation, vibration, sonication or
compression.
The parts of the mixture added at any of the stages may be any combination of
individual
ingredients or parts of individual ingredients. For instance, the ingredients
added in the first stage
may be all or part of each of the one or more materials A and one or more
materials B, all or part
of each of the one or more materials A, one or more materials B or one or more
materials C, all
or part of each of the one or more materials A, one or more materials B, one
or more materials
C, one or more materials D and/or one or more materials E, where materials A,
B, C, D, and E
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may be reactive, matrix, binder, conductive additive, and/or processing
additive materials in any
combination or order. All or some of said materials A, B, C, D, and/or E may
be present in the
initial stage of mixing. All or some of said materials A, B, C, D, and/or E
may be present in the
later stages of mixing. The conditions (e.g. mixing type, mixing rate, mixing
temperature etc.) of
the various mixing stages may be the same or different. The process mixture
may be sifted to
remove or collect particles of a specific size or size range between any of
the stages. Mixing may
also involve shearing. Mixing may be done also by spraying andor by shearing
and/or
calendering, e.g., in a nip between two or more rollers or compressing and/or
shearing between
two plates.
In one preferred embodiment of the invention, the number of mixing stages may
be two, material
A may be one or more active materials, material B may be one or more matrix
materials and
material C may be a one or more binder materials. Material A, material B, and
material C may
be mixed in stage 1 at specific process conditions, for a specific time in a
specific mixing
machine, the resulting process mixture may be mixed in stage 2 at specific
process conditions,
for a specific time in a specific mixing machine, and the process mixture may
be further mixed
in stage 3 at specific process conditions, for a specific time in a specific
mixing machine.
In one preferred embodiment of the invention, the number of mixing stages may
be three, material
A may be one or more active materials, material B may be one or more matrix
materials, material
C may be one or more binder materials, material D may be one or more
conductive additive
materials, and material E may be one or more processing additive materials,
material A and
material B may be mixed in stage 1 at specific process conditions, for a
specific time in a specific
mixing machine, the resulting process mixture may sifted to remove particles
larger than a certain
size, the resulting process mixture may be mixed in stage 2 together with
material C at specific
process conditions, for a specific time in a specific mixing machine, and the
process mixture may
be further mixed in stage 3 at specific process conditions, for a specific
time in a specific mixing
machine.
In one preferred embodiment of the invention, the number of mixing stages may
be three, material
A may be one or more active materials, material B may be one or more matrix
materials, material
C may be one or more binder materials, material D may be one or more
processing additive
materials, material A and material B may be mixed in stage 1 at specific
process conditions, for
a specific time in a specific mixing machine, the resulting process mixture
may be mixed in stage
2 together with material C and material D at specific process conditions, for
a specific time in a
specific mixing machine, and the process mixture may be further mixed in stage
3 at specific
process conditions, for a specific time in a specific mixing machine.
In one preferred embodiment of the invention, the number of mixing stages may
be N, where N
is greater than 2, material A may be one or more active materials, material B
may be one or more
matrix materials, material C may be one or more binder materials, material D
may be one or more
processing additive material, material A and material B may be mixed in stage
1 at specific
process conditions, for a specific time in a specific mixing machine, the
resulting process mixture
may be mixed in stage 2 together with material C and material D at specific
process conditions,
for a specific time in a specific mixing machine, and the process mixture may
be further mixed
in stage 3, together with material D, at specific process conditions, for a
specific time in a specific
mixing machine. Stage 4 and beyond may repeat the process of stage 3. Stage 3
mixing may be
accomplished by wetting, e.g. spraying, dipping or dripping, and may comprise
an additional step
of feeding the subsequent mixture through a nip between the rollers of a
calendar.
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A "paste" may be a substance that behaves as a solid until a sufficiently
large load or stress is
applied, at which point it flows like a fluid. A paste may be an example of a
Bingham plastic
fluid. Pastes may consist of a mixture of granular material in a liquid (the
background fluid).
Unlike a dispersion or slurry, in a paste the individual particles and/or
grains may be jammed
together like sand on a beach and/or may form a disordered, glassy or
amorphous structure, which
may give a paste a solid-like character. The background fluid of the paste
preferably is less than
85% and more preferably less than 70% and more preferably is less than 65% and
most preferably
is less than 60% by mass of the paste. Here, in contrast to a paste, a slurry
may describe a thin
sloppy mud or cement or, in general, any fluid mixture of a pulverized solid
with a liquid, which,
unlike a paste, may behave like a thick fluid and/or, which may flow under
gravity.
In some embodiments of the invention, the paste may comprise less than 50%
background fluid.
In some embodiments of the invention, the paste may comprise less than 40%
background fluid.
In some embodiments of the invention, the paste may comprise less than 30%
background fluid.
In some embodiments of the invention, the paste may comprise less than 20%
background fluid.
In some embodiments of the invention, the paste may comprise less than 10%
background fluid.
In some embodiments of the invention, the paste may comprise less than 5%
background fluid.
In some embodiments of the invention, the paste may comprise less than 2%
background fluid.
In some embodiments of the invention, the paste may comprise less than 1%
background fluid.
In some embodiments of the invention, the paste may comprise less than 0.5%
background fluid.
In some embodiments of the invention, the paste may comprise less than 0.2%
background fluid.
In some embodiments of the invention, the paste may comprise less than 0.1%
background fluid.
In some embodiments of the invention, the paste may comprise greater than 50%
background
fluid. In some embodiments of the invention, the paste may comprise greater
than 40%
background fluid. In some embodiments of the invention, the paste may comprise
greater than
30% background fluid. In some embodiments of the invention, the paste may
comprise greater
than 20% background fluid. In some embodiments of the invention, the paste may
comprise
greater than 10% background fluid. In some embodiments of the invention, the
paste may
comprise greater than 5% background fluid. In some embodiments of the
invention, the paste
may comprise greater than 2% background fluid. In some embodiments of the
invention, the
paste may comprise greater than 1% background fluid. In some embodiments of
the invention,
the paste may comprise greater than 0.5% background fluid. In some embodiments
of the
invention, the paste may comprise greater than 0.2% background fluid. In some
embodiments of
the invention, the paste may comprise greater than 0.1% background fluid.
In some embodiments of the invention, the paste may comprise and combination
of any of the
upper and lower limits herein specified. In some embodiments of the invention,
the paste may
comprise between 85% and 0.1% background fluid. In some embodiments of the
invention, the
paste may comprise between 70% and 0.1% background fluid. In some embodiments
of the
invention, the paste may comprise between 65% and 0.1% background fluid. In
some
embodiments of the invention, the paste may comprise between 60% and 0.1%
background fluid.
In some embodiments of the invention, the paste may comprise between 55% and
0.1%
background fluid. In one embodiment, the paste may comprise between 50% and
0.1%
background fluid. In some embodiments of the invention, the paste may comprise
between 85%
and 0.2% background fluid. In some embodiments of the invention, the paste may
comprise
between 70% and 0.2% background fluid. In some embodiments of the invention,
the paste may
comprise between 65% and 0.2% background fluid. In some embodiments of the
invention, the
paste may comprise between 60% and 0.2% background fluid. In some embodiments
of the
invention, the paste may comprise between 55% and 0.2% background fluid. In
one embodiment,
the paste may comprise between 50% and 0.2% background fluid. In some
embodiments of the
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invention, the paste may comprise between 85% and 0.5% background fluid. In
some
embodiments of the invention, the paste may comprise between 70% and 0.5%
background fluid.
In some embodiments of the invention, the paste may comprise between 65% and
0.5%
background fluid. In some embodiments of the invention, the paste may comprise
between 60%
and 0.5% background fluid. In some embodiments of the invention, the paste may
comprise
between 55% and 0.5% background fluid. In one embodiment, the paste may
comprise between
50% and 0.5% background fluid. In one embodiment, the paste may comprise
between 50% and
0.2% background fluid. In some embodiments of the invention, the paste may
comprise between
85% and 1% background fluid. In some embodiments of the invention, the paste
may comprise
between 70% and 1% background fluid. In some embodiments of the invention, the
paste may
comprise between 65% and 1% background fluid. In some embodiments of the
invention, the
paste may comprise between 60% and 1% background fluid. In some embodiments of
the
invention, the paste may comprise between 55% and 1% background fluid. In one
embodiment,
the paste may comprise between 50% and 1% background fluid. In some
embodiments of the
invention, the paste may comprise between 85% and 2% background fluid. In some
embodiments
of the invention, the paste may comprise between 70% and 2% background fluid.
In some
embodiments of the invention, the paste may comprise between 65% and 2%
background fluid.
In some embodiments of the invention, the paste may comprise between 60% and
2% background
fluid. In some embodiments of the invention, the paste may comprise between
55% and 2%
background fluid. In one embodiment, the paste may comprise between 50% and 2%
background
fluid. In some embodiments of the invention, the paste may comprise between
85% and 5%
background fluid. In some embodiments of the invention, the paste may comprise
between 70%
and 5% background fluid. In some embodiments of the invention, the paste may
comprise
between 65% and 5% background fluid. In some embodiments of the invention, the
paste may
comprise between 60% and 5% background fluid. In some embodiments of the
invention, the
paste may comprise between 55% and 5% background fluid. In one embodiment, the
paste may
comprise between 50% and 5% background fluid.
A paste may be produced by applying one or more background fluids, liquids
and/or dispersants
to a powder or dry blend. In some embodiments of the invention, application of
background
fluid, liquid and/or dispersant may be via, for instance, a mixer. In some
embodiments of the
invention, application of background fluid, liquid and/or dispersant may be by
placing the powder
or dry blend under a wetter, such as a sprayer. In some embodiments of the
invention, application
of background fluid, liquid and/or dispersant may be via, for instance, a
mixer and/or by placing
the powder or dry blend under a wetter, such as a sprayer.
"Reactive material" here may be any material that chemically reacts, including
but not limited to
electrochemically, with another material. Active materials and/or active
material precursors may
be reactive materials according to the invention. A reactive material may be
in the form of
particles and/or grains. The reactive material may be a dry reactive material.
In a dry blend, paste
or film, the reactive material preferably comprises more than 40% and more
preferably more than
60% and most preferably more than 70% of the solid mass of the dry blend,
paste or film.
A "binder" here may mean any material or combination of materials that holds
or draws other
materials together to form a cohesive whole mechanically, chemically, or as an
adhesive. A
binder may bind materials, e.g. particles, inside films, e.g. electrodes
and/or between materials
in a film to a substrate, e.g. a current collector of an electrode. A binder
may be fibrillizable. A
binder may be fribrilized. Examples of binders include, but are not limited
to, e.g. thermoplastics,
including but not limited to polyethylene (PE), polypropylene (PP), such as
nylon, PLA
(Polylactic acid or polylactide), polybenzimidazole (PBI, short for Poly-[2,2'-
(m-phenylen)-5,5'-
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bisbenzimidazoleD, polycarbonate, polyether sulfone, polyetherether ketone,
polyetherimide,
polyethylene oxide (PEO), polyphenylene oxide, polyphenylene sulfide,
polypropylene,
polystyrene, polyvinyl chloride, acrylic polymers and their derivatives and
fluoropolymers and
any combination thereof. Examples of acrylic polymers and their derivative
include, but are not
limited to, Acrylic (poly(methyl methacrylate) or PMMA), ABS (acrylonitrile
butadiene
styrene), methacrylates, methyl acrylates, ethyl acrylates, 2-Chloroethyl
vinyl ether, 2-
Ethylhexyl acrylates, Hydroxyethyl methacrylates, butyl acrylates and butyl
methacrylates and
any combination thereof. Examples of fluoropolymers include, but are not
limited to,
polytetrafluoroethylenes (PTFEs), such as Teflon, polyvinylidene fluoride
(PVDF),
polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) and polyvinylidene
fluoride co-
polymers, polyvinylfluoride (PVF), polychlorotrifluoroethylene (PCTFE),
perfluoroalkoxy
polymer (PFA), fluorinated ethylene-propylene (FEP),
polyethylenetetrafluoroethylene (ETFE),
polyethylenechlorotrifluoroethylene (ECTFE), Perfluorinated Elastomer
(FFPM/FFKM),
Chlorotrifluoroethylenevinylidene fluoride FPM/FKM, Tetrafluoroethylene-
Propylene (FEPM),
Perfluoropolyether (PFPE) and Perfluorosulfonic acid (PFSA) and any
combination thereof. A
binder may be in the form of particles and/or grains. The binder may be a dry
binder. In a dry
blend, paste or film, the binder preferably comprises less than 15% and more
preferably less than
10% and more preferably less than 7% and more preferably less than 5% and more
preferably
less than 2% and most preferably less than 1% of the solid mass of the dry
blend, paste or film.
A binder may be mechanically processed into its final morphology in the dry
film, pasty film or
paste. A binder may be always in a solid state and/or never be dissolved, for
instance, in a solvent,
during processing or while in the dry film or paste.
"Active material" here may mean a reactive material that participates in a
reaction, for instance
an electrochemical reaction, in an electrochemical cell. Examples of active
materials include, but
are not limited to NaC1, NaF, Na2S03, Na2SiO3, Na4P207, NaA1C14, NaA1C14*xS02,
NaA1C14*1.5S02, NaA1C14*3S02, S02C12, SO2, C12, Ni, Cu, CuO, NiO, Cu2O, Fe,
FeO, Fe2O3,
Fe304, steel, NiF2, NiC12, FeCl2, FeCl3, FeF2, FeF3, CuC12, CuCl, CuF2, CuF,
porous carbon,
Lithium mixed oxides and Lithium mixed phosphates, such as lithium iron
phosphate (LFP),
Lithium Manganese Iron Phosphate (LMFP), Lithium Nickel Cobalt Manganese oxide
(NCM),
Lithium Nickel Cobalt Aluminium oxides (NCA), Lithium Manganese oxide (LMO),
Lithium
Cobalt oxide (LCO) and combinations thereof. "x: in NaA1C14*xS02 may be any
number
between 1 and 5. An active material may be in the form of particles and/or
grains. The active
material may be a dry active material. An active material may be always in a
solid state and/or
never be dissolved in a solvent during processing or in the dry film.
"Active material precursor" (also termed "precursor material") here may mean a
material, which
may be a reactive material, that may act as a precursor to an active material.
Examples of
precursor materials include, but are not limited to Na2S03, Na2SiO3, Na4P207,
Ni, Cu, Fe, porous
carbon, Cu(OH)2, Fe(OH)2, Cu2CO3(OH)2, Cu(HC00)2 and combinations thereof. A
precursor
material may be in the form of particles and/or grains. The active material
may be a dry precursor
material. A precursor material may be always in a solid state and/or never be
dissolved in a
solvent during processing or in the dry film.
"Matrix material" here may mean a material that may serve as a mechanical
support and/or
available surface and/or a conduit (e.g. an electrical conduit), for enabling
or promoting
formation and/or dissolution of reactive materials (e.g. active materials
and/or precursor
materials). A matrix material is preferably not consumed during the
electrochemical reaction of
the electrochemical device. A matrix material may be electrically conductive
or non-conductive
and/or catalytic or non-catalytic. Examples of matrix materials include, but
are not limited to,
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carbon and/or allotropes of carbon. Examples include, but are not limited to
ketjen black,
graphite, hard carbon, nanotubes, nanofibers, carbon nanotubes, carbon
nanofibers, carbon
nanobuds, activated carbon, reduced graphene oxide, celite, humic acid,
diatomaceous earth, Ni,
Cu, Fe, steel, brass, clays, bentonite, caolinite, Ni foam, Cu foam, Al foam,
steel wool, Ni-plated
metal, Fe-plated metal, microfibers, glass fiber, quartz fibers, basalt
fibers, polyamide fibers,
polyethylene fibers, polypropylene fibers and any combination thereof. A
matrix material may
be in the form of particles and/or grains. The matrix material may be a dry
matrix material. In a
dry blend, paste or film, the matrix preferably comprises less than 60% and
more preferably less
than 40% and most preferably less than 30% of the solid mass of the dry blend,
paste or film. A
matrix material may be always in a solid state and/or never be dissolved in a
solvent during
processing or in the dry film, pasty film or paste.
A "Reactive material ¨ matrix material composite" (also termed "reactive
composite") here may
mean a dry mixture or paste comprising, at least, reactive material and matrix
material. When the
reactive material is an active material, the reactive composite may be an
"active material ¨ matrix
material composite" (also termed "active composite"). When the reactive
material is an active
material precursor (precursor material), the reactive composite may be an
"precursor material ¨
matrix material composite (also termed "precursor composite"). Any of the
reactive composites
may further comprise additional materials such as conductive additives and/or
binders. A reactive
composite may be in the form of particles and/or grains. The reactive
composite may be a dry
reactive composite. A reactive composite may be always in a solid state and/or
never be dissolved
in a solvent during processing or in the dry film, pasty film or paste.
"Composite" here may mean a dry mixture or paste of a matrix material and at
least one other
material. A composite may comprise, for instance, a matrix material and a
binder and/or a
reactive material and/or a conductive additive. The mixture may mean a dry
blend or a wet
mixture.
A "Conductive additive" may mean a conductive material that enhances
conductivity of a
composite, dry mixture and/or dry blend. Enhanced conductivity here means
having an electrical
conductivity higher than before the enhancement. Examples of conductive
additives include, but
are not limited to conductive materials, e.g. metals, such as Ni, Cu, Fe, Al,
brass, steel, CuNi
alloys, Ag or metal like materials, such as carbon nanomaterials, e.g.
graphene, graphite,
nanotubes, fullerenes, carbon nanobuds, glassy carbon and/or carbon nanofoam,
carbon
nanowires and/or reduced graphene oxide and any combination thereof. A
conductive additive
may be in the form of particles and/or grains. Said particles and/or grains
may be in the form of,
e.g., spheres, rods, tubes and/or flakes. The conductive additive may be a dry
conductive additive.
A conductive additive may be always in a solid state and/or never be dissolved
in a solvent during
processing or in the dry film, pasty film or paste.
"Fibrillizable" here means capable of being fibrillized (also called
fibrillated). "Fibrillizee
("fibrillated") means to be converted into, or furnished with fibrils. A
"fibril" here may be a fine
fiber or filament. A binder may be fribrillizable and/or fibrillized.
Fibrililization may be wet or
dry fribrillization. Examples of fibrilizable materials include, but are not
limited to high aspect
ratio particles, thermoplastics, including but not limited to Acrylic
(poly(methyl methacrylate) or
PMMA), ABS (acrylonitrile butadiene styrene), nylon, PLA (Polylactic acid or
polylactide),
polybenzimidazole (PBIõ short for
Poly-[2,2'-(m-phenylen)-5,5'-bisbenzimidazole]),
polycarbonate, polyether sulfone, polyetherether ketone, polyetherimide,
polyethylene,
polyphenylene oxide, polyphenylene sulfide, polypropylene, polystyrene,
polyvinyl chloride and
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fluoropolymers. Examples of fluoropolymers include, but are not limited to,
polytetrafluoroethylenes (PTFEs), such as Teflon.
"Processing additive" here means any additive that aids in processing of a
material but
substantially does not serve a function in the final product. A processing
additive may include a
material which is added during the electrode manufacturing process and
subsequently removed
at any stage before assembly of the electrochemical device. Examples of
processing additives
may include but are not limited to lubricants, surfactants, plasticizers,
dispersants (e.g. solvents,
suspendants or colloidants) and/or background fluids in pastes. Other
processing additives are
possible according to the invention. In general, any intentionally added
material that does not
serve a function in the final product may be termed a processing additive.
"Processing" here may mean, for instance, any process or process step carried
or with the aim of
transforming one or more of the raw materials into a process mixture, such as
a dry blend or a
paste, a mixture, a film, such as a dry film or a pasty film, an article, an
electrode, such as an
anode (12a) or a cathode, an electrochemical device such as an electrochemical
cell, such as a
battery or supercapacitor or any element thereof. Examples of processing steps
include, but are
not limited to, extruding, bonding, removing, fibrillizing, mixing, applying,
adhering,
calendaring and/or any other processing step present according to the various
embodiments of
the invention.
"Removal" (i.e. separation of liquids from solids) in the case of background
fluids and/or
dispersants, such as solutes, suspendants or colloidants, may be by any means
known in the art.
Removal may be by, for instance, mechanical separations (e.g. filtration and
centrifugation).
Removal may be by, for instance, diffusional separation (e.g. distillation,
absorption, extraction).
Removal may be by, for instance, membrane separation. Examples of removal
mechanisms
include, but are not limited to, evaporation, drum drying, filtration,
chemical reaction,
precipitation, crystallization, extraction, compression, acceleration,
deceleration, centrifugation,
impaction and/or solidification. Evaporation may be carried out by any means
known in the art,
including, but not limited to vibration, sonification, heating, vacuuming,
spray drying, freeze
drying, fluidized bed drying, supercritical drying and/or depressurization.
"Freestanding" here may mean able to fully or partially support itself and/or
be essentially free
of support or attachment for at least a portion of its length.
"Powder" here may mean a dry, bulk solid granular material composed of a large
number of
particles and/or grains that may flow freely when shaken or tilted.
"Film" here may mean a structure, e.g. a sheet, having one dimension (e.g.
thickness)
significantly smaller than the other dimensions (e.g. length and/or width). A
"dry film" may mean
a film that is dry and/or comprises a dry blend. A "pasty film" may be a film
that is composed of
a paste. Dry films and/or pasty films may be freestanding and/or supported,
for instance, on a
substrate, for instance a temporary substrate and/or a final substrate.
An "Adhesive substrate" here may mean any substrate having an adhesion
enhancing surface or
morphology. Examples include, but are not limited to, a solid or perforated
sheets, foams,
networks, sintered powders or agglomerates or meshes of material. A final
substrate may be an
adhesive substrate.
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"Adhesion enhancing surface or morphology" here may mean a material surface
and/or
morphology that physically, mechanically and/or chemically enhances the
adhesion of said
surface or morphology to another material, e.g. a reactive material, an active
material a precursor
material, a matrix material, conductive additive, a binder, a reactive
composite, an active
composite, a precursor composite and/or a powder, a paste and/or a film. Said
film may comprise
a matrix material, a binder, a conductive additive, reactive material, an
active material a precursor
material, a matrix material, a reactive composite, an active composite and/or
a precursor
composite, and/or a powder, which may comprise a matrix material, a binder, a
conductive
additive, reactive material, an active material a precursor material, a matrix
material, a reactive
composite, an active composite and/or a precursor composite. Examples of
adhesion enhancing
surfaces or morphologies include, but are not limited to, meshes or porous
materials, rough and/or
textured surfaces and/or coated surfaces. Such surfaces, voids, channels, gaps
dips and/or
protrusions in such surfaces may, for instance, provide improved adhesion to,
for instance, an
applied dry blend, paste, film, matrix material, binder, conductive additive,
reactive material,
active material, active material precursor, reactive composite, active
composite and/or precursor
composite and/or increased surface area for interaction, e.g., adhesion,
reaction and/or charge
transfer to said dry blend, paste, film, matrix material, binder, conductive
additive, reactive
material, active material, active material precursor, reactive composite,
active composite and/or
precursor composite.
"Mesh or porous material" here may mean a sheet having patterned or
unpatterned voids,
channels, passages or holes. A mesh or porous material may be produced, for
instance, by making
patterned or unpatterned holes or cuts into a solid planar metallic sheet by
e.g., molding, stamping
or other mechanical means, by weaving or otherwise intermingling strands of
material, by
compressing, e.g. particles and/or grains of material, by chemical addition or
removal, e.g. by
etching, or by any other means. The mesh or porous material may have a 3-
dimensional
morphology. A mesh or porous material may be produced, for example, by making
patterned cuts
into a sheet, and then stretching it so as to transform the cuts into holes.
"Textured surface" here may mean a surface having a multitude of voids
channels, gaps dips
and/or protrusions. Said voids, channels, gaps dips and/or protrusions may be
patterned, repeating
or random. A textured surface may be produced, for instance, by making
patterned or unpatterned
indentations, punctures or scrapes into a solid planar metallic sheet by e.g.,
molding, stamping or
other mechanical means, by chemical addition or removal, e.g. by etching, or
by any other means.
The textured surface may be a rough surface.
"Rough" here may mean having a coarse or uneven surface, as from, e.g.,
projections,
irregularities, or breaks. Preferably, the roughness, as measured in terms of
roughness value (Ra),
is 0.25 microns or above.
"Adhered to or otherwise coupled with" here may refer to bonded and/or
mechanically
interlocked, wedged and/or otherwise intermingled. Bonding can be, for
instance by dry bonding,
chemical adhesion, dispersive adhesion and/or diffusive adhesion. Mechanically
interlocking can
be, for instance, by filling voids, channels or pores of the surfaces or bulk
material and/or
surrounding fibers or threads at the surface or in the bulk material. Adhesion
or coupling can be
achieved by applying a material as a powder, dry blend, paste or film on both
sides of a mesh or
porous material such that, upon application, the material applied to one side
of the mesh and/or
porous material touches and/or bonds to the material applied to the other side
of the mesh or
porous material. A film and/or a process mixture may be adhered to or
otherwise bonded to a
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"Self adhesion" may mean when two components of the same or similar material
(for instance
two same or differing compositions of process mixtures or two same or
different compositions
for films) adhere to one another. In the case of, for instance, a mesh or
porous substrate or any
substrate that has sufficiently large pores, gaps, holes, voids or channels to
allow one or more
continuous pathways from one side of the substrate to the other, two films can
be adhered to or
otherwise coupled with the substrate by self adhesion through one or more of
the pores, gaps,
holes, voids or channels. Thus, the films may, at least partially, be adhered
to or otherwise
coupled with the substrate by self adhesion.
"Dry bonding" here may describe bonding my means of heat and/or pressure. Dry
bonding may
be in the absence of liquids and/or chemical reaction during bonding.
"Electrode functionality" here may mean enabling, promoting or otherwise
facilitating oxidation
and/or reduction reactions, charge transfer, or other electrochemical
functions of the electrode,
e.g. the anode and/or cathode, within an electrochemical cell.
A "High Aspect Ratio Particle" here may mean here particles having one
dimension significantly
larger than the other dimensions of the particle. The high aspect ratio
particles may be conductive
or non-conductive. Examples of High Aspect Ratio Particle include but are not
limited to
conductive flakes, chips, fibers, tubes, ribbons, rods and/or strings. The
smallest dimension of
the structure may be of nanometer scale or above. The largest dimension may be
of micron scale
or below. The ratio of the largest dimension to the smallest dimension may be
greater than 2 and
more preferably greater than 4 and more preferably greater than 10 and more
preferably greater
than 20 and more preferably greater than 50 and most preferably greater than
100. Examples of
high aspect ratio particles include, but are not limited to, carbon nanotubes
(CNTs), fullerene
functionalized carbon nanotubes, such as NanoBuds (CNBs), graphene, graphite,
carbon
nanoribbons and metal flakes, chips, fibers, tubes, rods and/or strings. Other
materials and
morphologies that have a high aspect ratio and are conductive are possible
according to the
invention. A conductive pathway of high aspect ratio particles may mean two or
more conductive
high aspect ratio particles in contact, creating an essentially continuous
conductive network
extending over a distance longer than the longest dimension of an individual
high aspect ratio
particle.
While the foregoing examples are illustrative of the principles of the present
invention in one or
more particular applications, it will be apparent to those of ordinary skill
in the art that numerous
modifications in form, usage and details of implementation can be made without
the exercise of
inventive faculty, and without departing from the principles and concepts of
the invention.
Accordingly, it is not intended that the invention be limited, except as by
the claims set forth
below.
Figure 1A shows an embodiment of the invention wherein a process mixture (9),
such as a dry
blend (1) or paste (2), for use in and/or for the manufacture of an article
(10) used in an
electrochemical device, comprises one or more reactive materials (3) and/or
reactive composites
(4). The reactive composite, when present, may comprise one or more reactive
materials (3) and
one or more matrix materials (5). The dry blend (1) or paste (2) may further
comprise one or
more binders (6). One or more of the reactive materials may comprise one or
more active
materials (3a) and/or one or more precursor materials (3b). The precursor
material (3b) may be a
precursor to an active material (3a). The process mixture (9) may further
comprise one or more
conductive additive (7). The conductive additives may form a conductive
pathway through all or
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part of the material. In the embodiment of Figure 1A, the binder (6) may be
distributed around
the other materials (reactive materials (3, 3a, 3b), reactive composites (4,
4a, 4b), conductive
additives (7)). According to one aspect of the invention, this may occur, for
instance, before,
during or after processing when the binder (6) may become fully or partially
fibrillized. In such
a circumstance, some or all of said other (non-binder) materials may be in the
form of particles
and/or grains and/or are in solid phase. The process mixture (9) may comprise
substantially no
non-fibrillizable binders.
The use of multiple binders (6) in a given process mixture (9) is advantageous
in some cases. In
particular, binders (6) with differing melting points have been surprisingly
found to have a
synergistic effect. As an exemplary embodiment, a binder (6) may comprise both
teflon (PTFE)
and polyethylene-oxide (PEO). This combination has been found to be
particularly effective for
Li-ion cathodes (12b). When pure PTFE binder is used with a Li-ion cathodic
active material at
120 C compounding temperature, along with 6% conductive carbon additives, the
obtained
electrode material has 1.4 g/cm3 density. When PEO:PTFE binders are used in
1:1 ratio on the
same cathodic active material at same 120 C compounding temperature and same
amount of
carbon additives, the obtained electrode material has 1.7 g/cm3 density. This
densification is
attributed to the reduced viscosity of the compounded electrode material. The
resulting electrode
material can be further densified by calendering. Moreover, at 120-160 C
processing
temperature range, the PEO:PTFE binder has been found to create stronger
adhesion to the
current collector than pure PTFE binder. This stronger adhesion is attributed
to the lower melting
point of PEO. While the use of PEO creates these advantages, it is not a
suitable binder on its
own. Without intending to be bound by theory, the need for the presence of
PTFE is attributed to
its better fibrillizing properties, and furthermore its cathodic chemical
stability is advantageous
for the electrode longevity. The synergistic advantages of blended binder
materials are surprising.
Other combinations, including binders and binder ratios, of multiple binders
are allowed by the
invention.
The dry blend (1) may comprise substantially no liquids. The dry blend (1) may
be a dry power.
All or part of the individual constituents of the dry blend may be dry before,
during, and/or after
processing. The reactive materials (3) may be dry reactive materials before,
during, and/or after
processing. The reactive composites may be dry reactive composites before,
during, and/or after
processing. The binders may be dry binders before, during, and/or after
processing. The
conductive additives may be dry conductive additives before, during, and/or
after processing.
The matrix material (5) may be a dry matrix material before, during, and/or
after processing. The
dry blend may be made from a paste.
Figure 1B shows an embodiment of the invention wherein, in the process mixture
(9), such as a
dry blend (1) or paste (2), some or all of the reactive materials (3, 3a, 3b)
and/or some or all of
the reactive composites (4, 4a, 4b) and/or some or all of the matrix materials
(5) and/or some or
all of the binders (6) and/or some or all of the conductive additives (7)
and/or any combination
thereof are in the form of particles and/or grains and/or are in solid phase.
According to one
aspect of the invention, this may occur, for instance, before, during or after
processing when the
binder (6) has not or has not yet become fully or partially fibrillized.
The dry blend (1), as shown in Figures 1A and 1B may comprise substantially no
processing
additives or other intentionally added material.
Figure 1C shows an embodiment of the invention wherein a paste (2) for use in
and/or for the
manufacture of an article (10) used in an electrochemical device, comprises
one or more reactive
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materials (3) and/or reactive composites (4) and a background liquid (8). The
reactive composite,
when present, may comprise one or more reactive materials (3) and one or more
matrix materials
(5). The process mixture (9), such as a dry blend (1) or paste (2), may
further comprise one or
more binders (6) One or more of the reactive materials may comprise one or
more active
materials (3a) and/or one or more precursor materials (3b). The precursor
material (3b) may be a
precursor to an active material (3a) The paste (2) may further comprise one or
more conductive
additives (7). The conductive additives may form a conductive pathway through
all or part of the
material. In the embodiment of Figure 1C, the binder (6) may be distributed
around the other
materials (reactive materials (3, 3a, 3b), reactive composites (4, 4a, 4b),
conductive additives
(7)). According to one aspect of the invention, this may occur, for instance,
before, during or
after processing when the binder (6) may become fully or partially
fibrillized. In such a
circumstance, some or all of said other (non-binder) materials may be in the
form of particles
and/or grains and/or are in solid phase. The paste (2) may comprise
substantially no non-
fibrillizable binders
Figure 1D shows an embodiment of the invention wherein, in the paste (2) some
or all of the
reactive materials (3, 3a, 3b) and/or some or all of the reactive composites
(4, 4a, 4b) and/or some
or all of the matrix materials (5) and/or some or all of the binders (6)
and/or some or all of the
conductive additives (7) and/or any combination thereof are in the form of
particles and/or grains
and/or are in solid phase. According to one aspect of the invention, this may
occur, for instance,
before, during or after processing when the binder (6) has not or has not yet
become fully or
partially fibrillized.
The paste (2) may have the same composition as the dry blend except for the
addition of one or
more background fluids (8). The paste (2) may comprise less than 85% liquid
and/or background
fluid (8) by mass. A dry blend (1) may be derived from a paste (2). A dry
blend (1) may comprise
substantially no processing additives or other intentionally added material.
Figure 2a shows an embodiment an article (10) of the invention for use in an
electrochemical
device (40). The article (10) may comprise a dry film (11a), alone or in
combination with one or
more additional elements. The dry film (11a) may comprise a dry blend (1) of
the invention
and/or be derived from the process mixture (9), such as the dry blend (1)
and/or paste (2), of the
invention. The dry film (11a) may comprise one or more reactive materials (3)
and/or reactive
composites (4) The reactive composite, when present, may comprise one or more
reactive
materials (3) and one or more matrix materials (5). The dry film (11a) may
further comprise one
or more binders (6) The dry film (11a) may further comprise one or more
conductive additives
(6). The dry film (11a) may be continuous. The dry film (11a) may be self-
supporting or a
freestanding film (11c). The dry film (11a) may be adhesive. Some or all of
the one or more
conductive additives (7) may make direct ohmic contact within the dry film so
as to form one or
more conductive pathways within the dry film (11a). The dry film (11a) may be
an element of an
electrode (12), i.e., an anode (12a) and/or a cathode (12b). The electrode may
be part of an
electrochemical device (40). The dry film (11a) may be bonded to, adhered to
or otherwise
coupled with a final substrate (32b) The final substrate (32b), such as an
adhesive substrate (14),
which may be a solid or perforated sheet, foam, network, sintered powder or
agglomerate or mesh
of material, may be electrically conductive and/or may have an adhesion
enhancing surface (15)
and/or morphology (16). The adhesion enhancing surface may comprise a chemical
or physical
adhesion promoter and/or may have a rough and/or porous and/or textured
surface (18). The
adhesion enhancing morphology may contain voids and/or channels (19). Some or
all of these
voids and/or channels (19) may become fully or partially filled with dry film
(I la) material and/or
dry blend (1), some of which may be directly connected to the bulk dry film
(11a) The final
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substrate (32b) may be a current collector (17) which may be an anodic current
collector (17a)
or cathodic current collector (17b). The dry film (11a) bonded to, adhered to
or otherwise coupled
with the current collector (17), may be an electrode (12), e.g., and anode
(12a) and/or a cathode
(12b). Said anode (12a) and/or cathode (12b) may be used in an electrochemical
device (40).
Figure 2b shows an embodiment of the invention in which some or all of the
reactive material
(3) and/or reactive composite (4), matrix material (5) and binder (6) may be
intermixed within
the dry film (11a) with a first ratio (11a1), wherein some of the reactive
material (3) and/or
reactive composite (4), matrix material (5) and binder (6) may be intermixed
within the dry film
with at least one opposing different second ratio (1 1a2), wherein the first
ratio of materials
provides enhanced electrode functionality, and wherein the second ratio of
materials provides
enhanced adhesive functionality.
Figure 2b also shows an embodiment of the invention in which some or all of
the conductive
additive (7) may be intermixed within the dry film (11a) with a first ratio
(11a3), wherein some
of the conductive additive (7) may be intermixed within the dry film (11a)
with at least one
opposing different second ratio (11a4), wherein the second ratio provides
higher conductivity
than the first ratio.
Figure 2c shows an embodiment of the invention in which the ratio of reactive
material (3) and/or
reactive composite (4) and/or matrix material (5) and/or binder (6) and/or the
conductive additive
(7) may be distributed within the dry film (11a) with a gradually changing
gradient (11a5)
between the starting composition (11a6) and the ending composition (1 1a7) of
one or more of
the reactive materials (5) and/or reactive composites (4) and/or matrix
materials (5) and/or
binders (6) and/or conductive additive (7).
Figures 2d-2f show various embodiments of the invention wherein the pasty film
(lib) may be
deposited on the final substrate (32b), such as an adhesive substrate (14),
which may be a solid
or perforated sheet, foam, network, sintered powder or agglomerate or mesh of
material, may be
electrically conductive and/or may have an adhesion enhancing surface (15)
and/or morphology
(16) Subsequently or simultaneously, the background fluid (8) may be removed
(13) to create a
dry film (1 la) which may be adhered to the final substrate (32b).
Figure 2d shows an intermediate step in producing an article (10) of the
invention for use in an
electrochemical device (40). Said article is here termed a pre-article (101).
The pre-article (101)
may comprise a pasty film (1 lb), alone or in combination with one or more
additional elements.
The pasty film (1 lb) may comprise a paste (2) of the invention. The pasty
film (11b) may
comprise one or more reactive materials (3) and/or reactive composites (4).
The reactive
composite, when present, may comprise one or more reactive materials (3) and
one or more
matrix materials (5). pasty film (1 lb) may further comprise one or more
binders (6). The pasty
film (1 lb) may further comprises one or more conductive additives (6) The
pasty film (1 lb) may
further comprise one or more background fluids (8). The pasty film (1 lb) may
be continuous.
The pasty film (lib) may be self-supporting or a freestanding film (11c) The
pasty film (1 lb)
may be adhesive. Some or all of the one or more conductive additives (7) may
make direct ohmic
contact within the dry film so as to form one or more conductive pathways
within the pasty film
(1 lb). The pasty film (1 lb), when the background fluid (8) may be removed
(13) may be an
element of an electrode (12), such as an anode (12a) and/or a cathode (12b).
The anode (12a)
and/or cathode (12b) may be part of an electrochemical device (40). The pasty
film (1 lb) may be
bonded to, adhered to or otherwise coupled with a final substrate (32b), which
may an adhesive
substrate (14), such as a solid or perforated sheet, foam, network, sintered
powder or agglomerate
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or mesh of material, may be electrically conductive and/or may have an
adhesion enhancing
surface (15) and/or morphology (16). The adhesion enhancing surface may
comprise a chemical
or physical adhesion promoter and/or may have a rough and/or porous and/or
textured surface
(18). The adhesion enhancing morphology of the final substrate (32b) may
contain voids and/or
channels (19) Some or all of these may become fully or partially filled with
pasty film (1 lb)
material and/or paste (2), some of which may be directly connected to the bulk
pasty film (1 lb).
The final substrate (32b) may be a current collector (17), such as an anodic
current collector (17a)
or cathodic current collector (17b). Once the background fluid (8) is removes
(13), the resulting
dry film (11a) bonded to, adhered to or otherwise coupled with the collector
(17) may be an anode
(12a) or a cathode (12b). Said anode (12a) and/or cathode (12b) may be used in
an
electrochemical device (40).
Figure 2e shows an embodiment of the invention in an intermediate state
according to one
embodiment of the invention in which some or all of the reactive material (3)
and/or reactive
composite (4), matrix material (5) and binder (6) may be intermixed within the
pasty film (1 lb)
with a first ratio (1 lbl), wherein some of the reactive material (3) and/or
reactive composite (4),
matrix material (5) and binder (6) may be intermixed within the pasty film (1
lb) with at least one
opposing different second ratio (11b2), wherein the first ratio of materials
provides enhanced
electrode functionality, and wherein the second ratio of materials provides
enhanced adhesive
functionality.
Figure 2e also shows an embodiment of the invention in an intermediate state
according to one
embodiment of the invention in which some or all of the conductive additive
(7) may be
intermixed within the pasty film (lib) with a first ratio (11b3), wherein some
of the conductive
additive (7) may be intermixed within the pasty film (1 lb) with at least one
opposing different
second ratio (11b4), wherein the second ratio provides higher conductivity
than the first ratio
Figure 2f shows an embodiment of the invention in an intermediate state
according to one
embodiment of the invention in which the ratio of reactive material (3) and/or
reactive composite
(4) and/or matrix material (5) and/or binder (6) and/or the conductive
additive (7) may be
distributed within the pasty film (1 lb) with a gradually changing gradient
(11b5) between the
starting composition (11b6) and the ending composition (11b7) of one or more
of the reactive
materials (3) and/or reactive composites (4) and/or matrix materials (5)
and/or binders (6) and/or
conductive additive (7)
Figures 3 and 4 show several embodiments of the method for producing a dry
film (11) or an
article (10) according to the invention. The described embodiments of the
method for making a
dry film (11) or an article (10) for an electrochemical device (40), comprise,
at least, the steps of:
i. mixing at least one or more reactive materials (3) and/or reactive
composites (4) and
one or more binders (6) to form a process mixture (9), such as a dry blend (1)
or
paste (2); and
ii. forming (23) the process mixture (9) to produce one or more films (11),
such as one
or more dry films (11a) and/or one or more pasty films (11b).
Details of certain embodiments of step i) are shown in Figure 3. Details of
certain embodiments
.. of step ii) are shown in Figure 4.
Figure 3a shows one embodiment of the method in which one or more reactive
materials (3)
and/or reactive composites (4) and one or more binders (6) are mixed (21) in a
mixing vessel (20)
with a mixer (22) to form a process mixture (9) or one or more reactive
materials (3) and one or
more matrix material (5) are mixed (21) in a mixing vessel (20) with a mixer
(22) to form a
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reactive composite (4). Any means of mixing (22) are possible according to the
invention. During
the mixing (31) some or all of any fibrillizable binder (6) may fully or
partially fibrillize due to,
for instance, the shearing (41), where shear forces generated in the mixing
process, depending on
the operation of the mixer (22), the type of mixing (21) (e.g., shaking,
milling, grinding, shearing,
sonicating, shaking, vibrating, mortaring, tumbling, fluidizing and/or
stirring), and/or the
duration, speed and temperature of the mixing (21). Depending on the liquid
content of the
mixture, the mixture may be, for instance, a dry blend (1) or a paste (2). In
some embodiments,
one or more of the reactive materials (3), reactive composites (4), matrix
materials (5) and/or
binders (6) may be added dry, as a paste or as a dispersion (27), e.g., as a
solution (27b), a
suspension (27a) or a colloid (27c). In some embodiments, one or more of the
reactive materials
(3), reactive composites (4), matrix materials (5) and/or binders (6) may be
added as dry reactive
materials (3), dry reactive composites (4), dry matrix materials (5) and/or
dry binders (6). Said
dry materials may be in the form of particles and/or grains and/or as one or
more powders. In
some embodiments one or more of the reactive materials (3), reactive
composites (4), matrix
materials (5) and/or binders (6) may be added as particles and/or grains of
materials. In some
embodiments one or more of the reactive materials (3), reactive composites
(4), matrix materials
(5) and/or binders (6) may be added as dry and/or wet particles and/or grains
of materials and/or
as a dispersion (27) or paste (2). In some embodiments one or more of the
reactive materials (3),
reactive composites (4), matrix materials (5) and/or binders (6) may be added
as one or more
powders. Any combination of the above is possible according to the invention.
Figure 3b shows an embodiment of the invention wherein a conductive additive
(7) and/or a
matrix material (5) and/or a background fluid (8) is additionally mixed (21)
into the process
mixture (9) or wherein a conductive additive (7) and/or a binder (6) and/or a
background fluid
(8) is additionally mixed (21) into the reactive composite (4). According to
one aspect of the
invention, any or all of the conductive additive (7), binder (6) and/or a
matrix material (5) may
be dry, in a paste or in a dispersion (27), e.g. a solution (27b), a
suspension (27a) or a colloid
(27c) or may be as a dry material. Said dry materials may be in the form of
particles and/or grains
or as one or more powders. In some embodiments one or more of the conductive
additive (7),
binder (6) and/or matrix material (5) may be added as dry and/or wet particles
and/or grains of
materials and/or as a dispersion (27) or paste (2).
Figure 3c shows an embodiment of the invention wherein a dispersant (25) (be
it an solvent (22b),
suspendant (22a) and/or colloidant (22c)) and/or a background fluid (8) from
one or more of a
dispersion (27) and/or paste (2) of one or more of the reactive materials (3),
reactive composites
(4), binders (6), conductive additive (7) and/or a matrix material (5) is
fully or partially removed
(13) so as to form a paste (2) or dry blend (1).
One or more of the reactive materials (3) may be an active material (3a) or a
precursor material
(3b). One or more of the reactive composites (4) may be active composites (4a)
or a precursor
composites (4b). The active composites and/or precursor composites may be
produced by mixing
(31) one or more matrix materials (5) with one or more active materials (3a)
and/or precursor
materials (3b) The mixing may be done by mixing of dry or dispersed active
material (3a) and/or
precursor material (3b) and matrix material (5). In the case where one or more
of said materials
are dispersed, the dispersion (27) may be, for instance, a solution (27b), a
suspension (27a) or a
colloid (27c). In the case where one or more of said materials are dry, one or
more of said
materials may be in the form of a powder. In the case of a powder, suspension
or colloid, any or
all of said materials may be in the form of particles and/or grains.
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Examples of reactive materials (3) include, but are not limited to NaCl, NaF,
Na2S03, Na2SiO3,
Na4P207, NaA1C14, NaA1C14*xS02 (e.g. NaA1C14*1.5S02 and/or NaA1C14*3 SO2),
S02C12, SO2,
C12, Ni, Cu, CuO, NiO, Cu2O, Fe, FeO, Fe2O3, Fe304, steel, NiF2, NiC12, FeCl2,
FeCl3, FeF2,
FeF3, CuC12, CuCl, CuF2, CuF, Cu(OH)2, Fe(OH)2, Cu2CO3(OH)2, Cu(HC00)2,
Lithium mixed
oxides and Lithium mixed phosphates, such as lithium iron phosphate (LFP),
Lithium Manganese
Iron Phosphate (LMFP), Lithium Nickel Cobalt Manganese oxide (NCM), Lithium
Nickel
Cobalt Aluminium oxides (NCA), Lithium Manganese oxide (LMO), Lithium Cobalt
oxide
(LCO) and combinations thereof or any combination thereof. Examples of active
materials (3a)
include, but are not limited to NaCl, NaF, Na2S03, Na2SiO3, Na4P207, NaA1C14,
NaA1C14*xS02
(e.g. NaA1C14*1.5S02 and/or NaA1C14*3S02), SO2C12, SO2, C12, Ni, Cu, CuO, NiO,
Cu2O, Fe,
FeO, Fe2O3, Fe304, steel, NiF2, NiC12, FeCl2, FeCl3, FeF2, FeF3, CuC12, CuCl,
CuF2, CuF,
Lithium mixed oxides and Lithium mixed phosphates, such as lithium iron
phosphate (LFP),
Lithium Manganese Iron Phosphate (LIVTP), Lithium Nickel Cobalt Manganese
oxide (NCM),
Lithium Nickel Cobalt Aluminium oxides (NCA), Lithium Manganese oxide (LMO),
Lithium
Cobalt oxide (LCO) and combinations thereof or any combination thereof.
Examples of precursor materials (3b) include, but are not limited to Na2S03,
Na2SiO3, Na4P207,
Ni, Cu, Fe, porous carbon, Cu(OH)2, Fe(OH)2, Cu2CO3(OH)2, Cu(HC00)2 or any
combination
thereof.
Examples of matrix materials (5) include, but are not limited to ketjen black,
graphite, hard
carbon, nanotubes, nanofibers, carbon nanotubes, carbon nanofibers, activated
carbon, reduced
graphene oxide, celite, humic acid, diatomaceous earth, Ni, Cu, Fe, steel,
brass, clays, bentonite,
caolinite, Ni foam, Cu foam, Al foam, steel wool, Ni-plated metal, Fe-plated
metal, microfibers,
glass fiber, quartz fibers, basalt fibers, polyamide fibers, polyethylene
fibers, polypropylene
fibers or any combination thereof.
Examples of binders (6) include but are not limited to theanoplastics,
including but not limited
to polyethylene (PE), polypropylene (PP), such as nylon, PLA (Polylactic acid
or polylactide),
polybenzimidazole (PBI, short for Poly-[2,2' -(m-phenylen)-5,5' -bi sb
enzimi dazol
polycarbonate, polyether sulfone, polyetherether ketone, polyetherimide,
polyethylene oxide
(PEO), polyphenylene oxide, polyphenylene sulfide, polypropylene, polystyrene,
polyvinyl
chloride, acrylic polymers and their derivatives and fluoropolymers and any
combination thereof.
Examples of acrylic polymers and their derivative binders include, but are not
limited to, Acrylic
(poly(methyl methacrylate) or PMMA), ABS (acrylonitrile butadiene styrene),
methacrylates,
methyl acrylates, ethyl acrylates, 2-Chloroethyl vinyl ether, 2-Ethylhexyl
acrylates,
Hydroxyethyl methacrylates, butyl acrylates and butyl methacrylates and any
combination
thereof. Examples of fluoropolymer binders include, but are not limited to,
polytetrafluoroethylenes (PTFEs), such as Teflon, polyvinylidene fluoride
(P'VDF),
polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) and polyvinylidene
fluoride co-
polymers, polyvinylfluoride (PVF), polychlorotrifluoroethylene (PCTFE),
perfluoroalkoxy
polymer (PFA), fluorinated ethylene-propylene (FEP),
polyethylenetetrafluoroethylene (ETFE),
polyethylenechlorotrifluoroethylene (ECTFE), Perfluorinated Elastomer
(FFPM/FFKM),
Chlorotrifluoroethylenevinylidene fluoride FPM/FKM, Tetrafluoroethylene-
Propylene (FEPM),
Perfluoropolyether (PFPE) and Perfluorosulfonic acid (PF SA) and/or any
combination thereof
Examples of conductive additives (7) include but are not limited to conductive
materials, e.g.
metals, such as Ni, Cu, Fe, Al, brass, steel, CuNi alloys, Ag or metal like
materials, such as
carbon nanomaterials, e.g. graphene, graphite, nanotubes, fullerenes, carbon
nanobuds, glassy
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carbon and/or carbon nanofoam, carbon nanowires, reduced graphene oxide and/or
any
combination thereof.
Examples of solvents include but are not limited to water, ethanol,
isopropanol, methanol,
acetone, N-methyl-2-pyrrolidone, methyl isobutyl ketone, pentane, hexane,
heptane, petroleum
ether, alkanes, toluene, xylene, SO2, NaA1C14*xS02 (e.g. NaA1C14*1.5S02 and/or
NaA1C14*3S02), benzene or any combination thereof.
Examples of suspendants include but are not limited to water, ethanol,
isopropanol, methanol,
acetone, N-methyl-2-pyrrolidone, methyl isobutyl ketone, pentane, hexane,
heptane, petroleum
ether, alkanes, toluene, xylene, NaA1C14*xS02 (e.g. NaA1C14*1.5502 and/or
NaA1C14*3502),
benzene or any combination thereof.
Examples of colloidants include but are not limited to water, ethanol,
isopropanol, methanol,
acetone, N-methyl-2-pyrrolidone, methyl isobutyl ketone, pentane, hexane,
heptane, petroleum
ether, alkanes, toluene, xylene, SO2, NaA1C14*xS02 (e.g. NaA1C14*1.5502 and/or
NaA1C14*3S02), benzene or any combination thereof.
"x" in NaA1C14*xS02 in any of the examples may be any number between 1 and 5.
One or more of the binders (6) may be fully or partially fibrillizable.
Essentially all of the one or
more binders (6) may be fibrillizable. Some or all of the binder (6) may be
fibrilized during the
processing.
The mixing (31) of the one or more matrix materials (5) with the one or more
active materials
(3a) and/or precursor materials (3b) and/or conductive additives (7) and/or
background fluids (8)
may be carried out, by any means known in the art. For instance, the mixing
(31) may be carried
out by dispersing (26) one or more of the matrix materials (5) and one or more
active materials
(3a) and/or precursor materials (3b) and/or one or more binders (6) and/or
conductive additives
(7) in one or more dispersants (25) to create a dispersion (27). Essentially
all of the one or more
of the dispersants (25) and/or some or essentially all of the dispersants (25)
may then be
essentially fully removed (13) to create a powder. Alternately, only part of
the dispersant (25)
may be removed (13) to create a paste (2), wherein the dispersant (25) may act
as a background
fluid (8). Alternately, the mixing (31) may be carried out substantially in
the absence of any
dispersant (25) to create a mixed powder (35). Alternatively, the mixing may
be carried out by
any of proceeding methods, further comprising the step of adding a background
fluid (8) to create
or optimize a paste (2). Some or all of the mixing (31) may be carried out by,
for instance shaking,
milling, grinding, shearing, sonicating, shaking, vibrating, mortaring,
tumbling, fluidizing and/or
stirring or by any other means known in the art. The dispersant (25) may be a
solvent (25a), a
suspendant (25b), and/or a colloidant (25c). The dispersion (27) may be a
solution (27b), a
suspension (27a) and/or a colloid (27c). The dispersing (26) may comprise
suspending (26a),
dissolving (26b) and/or colloiding (26c).
Some or all of the reactive materials (3), some or all of the reactive
composites (4), some or all
of the matrix materials (5), some or all of the binders (6), some or all of
the conductive additives
(7) and/or some of all of the process mixture (9), such as the dry blend (1)
or paste (2), are in the
form of particles and/or grains before and/or during and/or after the
mechanical forming (23) of
the process mixture (9) (e.g. the dry blend (1) or paste (2)) and/or the film
(11) (e.g. the dry film
(11a) and or pasty film (lib)).
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One or more of the dispersants (25) may be removed (13) by, for instance, but
not limited to,
evaporation, drum drying, filtration, chemical reaction, precipitation,
crystallization, extraction,
compression, acceleration, deceleration, centrifugation, impaction and/or
solidification.
Evaporation may be carried out by, for instance, but not limited to,
vibration, sonification,
heating, vacuuming, spray drying, freeze drying, fluidized bed drying,
supercritical drying and/or
depressurization. Heating may be, for instance, but not limited to,
convective, conductive,
vibrational, frictional and/or radiative heating.
As shown in the example method and apparatus embodiments of Figure 4a - 4g,
the method may
further comprise producing a film (11), such as a dry film (11a) and/or a
pasty film (lib), from
the process mixture (9), such as the dry blend (1) and/or paste (2). The
process mixture (9) may
be produced by any means, which may form a film (11). The process mixture (9),
film (11) (e.g.
the dry film (11a) and/or pasty film (1 lb)) may be applying the film (11) to
a substrate (32), such
as a temporary substrate (32a) and/or a final substrate (32b), such as a an
adhesive substrate (14),
such as a solid or perforated sheet, foam, network, sintered powder or
agglomerate or mesh of
material.
In general, the apparatus for manufacture of the article (10), such as the
film (11) may comprise
one or more film formers (38) and one or more material feeders (45) to feed
one or more process
mixtures (9) into film former (38). In the embodiments shown in Figures 4a -
4g, the film former
(38) is a calender, though other film formers, such as extruders (not shown),
are possible
according to the invention. Regarding material feeders (45), in the
embodiments shown in Figures
4a ¨ 4g, the process mixture (9) is simply placed at the top of the calender
and the calender
cylinder motion feeds the process mixture (9) into the film former (38). Other
feeding
mechanisms known in the art are possible according to the invention,
including, but not limited
to, screw, vibratory, rotary, belt, apron, reciprocating, variable rate
feeders.
In general, the apparatus for manufacture of the article (10), such as the
film (11) on a substrate
(32) may comprise one or more film appliers (39), one or more film feeders
(45) to feed one or
more films (11) into film applier (39). In the embodiments shown in Figures 4a
- 4g, the film
applier (39) is a calender, though other film appliers (39), such as
compression plates (not
shown), are possible according to the invention. Regarding film feeders (45),
in the embodiments
shown in Figures 4a ¨ 4g, the film (9) is fed by the film former. Other
feeding mechanisms known
in the art are possible according to the invention, including, but not limited
to roller-2-roll and
sheet feeders (not shown). Similarly, the substrate may be fed by any feeding
system known in
the art, including but not limited to roller-2-roll and sheet feeders (not
shown). The film forming
(42) calenders may be of different sizes and/or may be rotated at different
speeds so as to provide
a controlled shear force in the process mixture (9) and/or the film (11). One
or more of the film
forming (42) calenders may be heated and/or cooled. The surface of one or more
of the
calendering cylinders may be treated to improve or reduce adhesion.
Shown in Figure 4a is an embodiment of a method and an apparatus of the
invention in which a
film (11), such as a dry film (11a) and/or pasty film (1 lb), is produced by
calendering through a
gap formed by a first film forming (42) calendering cylinder (30a) and a
second film forming
(42) calendering cylinder (30b). As an example of an alternative, an extruder
(not shown) may
be used to form the dry film (11a) or pasty film (1 lb). Film forming (42)
calender cylinder (30a)
and film forming (42) calender cylinder (30b) may be of the same or different
diameter and/or
rotate at the same or different rotation rates such that the most proximate
surfaces may have the
same or different speeds. Thusly, a shear force may be controlled in the
process mixture (9) (e.g.
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the dry blend (1) and/or paste (2)) as it passes through the nip of the
calender. The larger
difference in speeds, the larger the shear force generated. The shear forces
generated in the mixer
(21), shearer (41) and/or film applier (39) may promote the fibrillization of
fibrillizable binders
present in the process mixture (9). The resulting film (11) may be a self-
supporting or a
freestanding film (11c) and/or a supported film (11d), which may be supported,
for instance, by
a substrate (32). A substrate may be a temporary substrate (32a) or a final
substrate (32b). A
substrate may be rigid or flexible. A final substrate (32b) may be, for
instance, an adhesive
substrate (14). A temporary substrate (32a), may be, for instance, a portion
of a first (30a) and/or
a second film forming (42) calendering cylinder (30b). In the examples shown
in the various
embodiments of Figure 4, the film forming (42) calendering cylinder (30b)
which simultaneously
acts as a temporary substrates (32a) is the second film forming (42)
calendering cylinder (30b),
however film forming (42) calendering cylinder (30a) may also serve as a
temporary substrate
(32a). A temporary substrate (32a) may also take the form of a, for instance,
a release liner (not
shown), which may be used to, for instance, store, process before transferring
or otherwise apply
the dry film (11a) or pasty film (lib) to a final substrate (32b), such as an
adhesive substrate
(14). A temporary substrate (32a) may be used, for instance, for transferring
a film (11), which
may be, for instance, a freestanding film (11c), or otherwise not yet
deposited and/or adhered to
a final substrate (32b). Other forms and implementations of temporary
substrates (32a) and final
substrates (32b) are possible according to the invention. In the corresponding
apparatus for
manufacture of the article (10) the film former (38) may comprise one or more
calenders
comprising at least two calendering cylinders (30a and 30b) in aligned
opposition to each other
with a pre-defined gap and/or force between the calendering cylinders (30a and
30b); and at least
one drive unit turning the calendering cylinders at controlled speed, wherein
the feeder (45) is
the motion of the calender, which provides the process mixture (9) to the gap
between the
cylinders so as to compress the process mixture (9) into a film (11).
The film (e.g. the dry film (11a) or pasty film (1 lb)) is applied to the
final substrate (32b) by any
means. A preferred means of applying said films is by mechanical compression
(37).
Additionally, shear forces can be generated by shearing (41) during the
application, which may
promote the fibrillization of fibrillizable binders present in the dry blend
(1), paste (2), dry film
(11a) and/or pasty film (1 lb). Figures 4a ¨ 4f show various embodiments of
the invention,
wherein the mechanical compression (37) is carried out by calendering between
two or more film
application (44) calendering cylinders (30a, 30b, 30c, 30d and 30e). Other
means are possible to
apply mechanical compression (37), including, but not limited to pressing the
dry film (ha) or
pasty film (11b) between two or more planar or contoured plates. A shearing
force can be added
to the mechanical compression (37), by shearing (41) by, for instance, moving
the planar and or
contoured plates in a planar direction while compressing. Any pair of film
forming (42) calender
cylinders and/or film application (44) calender cylinders may be of the same
or different diameter
and/or rotate at the same or different rotation rates such that the most
proximate surfaces may
have the same or different speeds. Thusly, a shear force may be applied in a
controlled manner
in the dry blend (1), paste (2), dry film (11a) and/or pasty film (11b) as it
passes through the nip
of each calender. The larger difference in speeds, the larger the shear force
generated during
shearing (41).
Figure 4a shows an embodiment with an optional film applicator (39) is a
separate calendering
mechanism consisting of film application (44) calendering cylinders (30d and
30e) aligned
opposition to each other with a pre-defined gap and/or force between the
calendering cylinders
and at least one drive unit turning the calendering cylinders at controlled
speed, wherein the
feeder (45) is the motion of the film forming (42) calender, which provides
the film (11) to the
gap between the cylinders so as to compress the film (11) into the substrate
(32). In this
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embodiment, one or more freestanding dry films (11a) or pasty films (1 lb) is
fed into the
calendering mechanism together with one or more final substrates (32b), which
may be an
adhesive substrate (14).
Figure 4b shows an embodiment in which one of the calendering cylinders (30b)
is
simultaneously part of a film applicator calender (39) and serves as a film
application (44)
calender cylinder (30c). In this embodiment of the invention, an additional
film application (44)
calendering cylinder (30d) is added to complete film application (44)
calendering mechanism
(39) Combined film formation (43) and film application (44) calender cylinder
(30b, 30c) also
acts as a temporary substrate (32a) for the film (11). In this embodiment of
the invention, film
application (44) calendering cylinder (30d) also serves as a temporary
substrate and substrate
feeder (46) for the final substrate (32b), which may be an adhesive substrate
(14). Calender (30c)
here also acts as part of the substrate feeder (46).
Figure 4c shows an embodiment similar to the embodiment of Figure 4b, however,
the film
foliner calendering mechanism (39) forces some or all of the dry blend (1),
paste (2), dry film
(11a) and/or pasty film (1 lb) into voids and/or channels (19) in the final
substrate (32b) such that
the dry blend (1), paste (2), dry film (11a) and/or pasty film (lib) is not a
distinct layer separate
from the final substrate (32b), which may be an adhesive substrate (14).
Figure 4d shows an embodiment similar to the embodiment of Figure 4b, however,
there are two
film former calendering mechanisms (38) and two film appliers (39) calendering
mechanisms
applying film (11) on two sides of the same substrate Here calendering
cylinders (30a1 and 30b1)
form a first film former (38a) and calendering cylinders (30a2 and 30b2) form
a second film
former (38b). Here also, calendering cylinders (30c1 and 30c2) form a film
applier (39).
Calendering cylinders (30b1 and 30c1) are one-in-the-same and calendering
cylinders (30b2 and
30c2) are one-in-the-same and serve as part of the film former (38) and film
applier (39).
Figure 4e shows an embodiment similar to the embodiment of Figure 4a, however,
an adhesive
substrate is fed through the film forming (42) calender (30a) such that film
forming (42) calender
(3a) also acts as a film application (44) calendering cylinder (30d). Thus,
the film former (38)
and the film applier (39) are one-in-the-same. In this embodiment, only a
single pair of
calendering cylinders are needed to both form and apply the dry film (11a) or
pasty film (1 lb).
Figure 4f shows an embodiment similar to the embodiment of Figure 4e, however,
an adhesive
substrate is fed between forming calenders (30a and 30b) such that a first dry
blend (la) or a first
paste (2a) is formed in a first dry film (11aa) or first pasty film (11ba) and
a second dry blend
(la) or a second paste (2a) is formed in a second dry film (11 ab) or a second
pasty film (1 lbb).
In this embodiment, only a single pair of calendering cylinders are needed to
both form and
deposit two dry films (1 laa and 1 lab) or pasty films (11ba and llbb). The
composition of the
first dry blend (la) or first paste (2a) may be the same or different that the
second dry blend (la)
or a second paste (2a).
Figure 4g shows an embodiment similar to the embodiment of Figure 4b, however,
having a
second film former (38) calender cylinder pair (30ab and 30bb) and a second
film applier (39)
calendering cylinder pair (30cb and 30db) forming and applying a second dry
film (11ab) and/or
second pasty film (1 lbb) from a second dry blend (lb) and/or a second paste
(2b), each being
separate and distinct from the first film forming (42) calender cylinder pair
(30aa and 30ba) and
a first film application (44) calendering cylinder pair (30ca and 30da)
forming and applying a
first dry film (11aa) and/or first pasty film (11ba) from a first dry blend
(la) and/or a first paste
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(2a). The properties (for example, but not limited to grain size, amount of
fibrillization,
composition, wetness and/or temperature) of the first dry blend (la) and/or a
first paste (2a) may
be the same or different from the properties of the second dry blend (lb)
and/or a second paste
(2b). The properties (for example, but not limited to thickness, grain size,
amount of fibrillization,
composition, wetness and/or temperature) of the first dry film (11 aa) and/or
a first pasty film
(2aa) may be the same or different from the properties of the second dry blend
(1lab) and/or a
second pasty film (11bb). By analogy, additional processing steps and
equipment (not shown)
may be added to produce additional dry blends (1), pastes (2), dry films (11a)
and/or pasty films
(lib) and apply them on top of previous additions. By this means, a multi-
layered dry film (11a)
and/or pasty film (11b) may be produced. By varying the properties of each
subsequent
application, the properties of the dry film (11a) and or pasty film (1 lb) may
be made to vary in
the direction perpendicular to the film and/or adhesive substrate. The same or
similar procedure
can be applied to any of the previous examples to achieve the same or similar
effects in the
product.
Another method according to the invention to achieve a same or similar effect
is to vary the
properties of the process mixture (e.g. the dry blend (1) and/or paste (2))
perpendicular to the
flow of material between the film foiming (42) calender cylinders in any of
the embodiments
presented.
According to the various embodiments of the invention, a shear force may be
applied, e.g. by
shearing (41), to all or part of the process mixture (9), such as the dry
blend (1) and/or paste (2),
and/or the components thereof, at any stage of the article (10) manufacturing
process. This may
be before and/or during and/or after mechanically compressing (37), shearing
(41), mixing (21),
and/or application to the substrate. This may be during the mixing of process
mixture (9). This
may be during film founation (43). This may be during the application of a
first or any subsequent
application processes. The application of shear force may fibrillizes some or
all of the one or
more fibrillizable binders.
Some or all of the process mixtures (9), one or more of the films (11), and/or
the components
thereof may be heated and/or cooled at any time or stage in the process, as
may be required to
achieve the various process ends. Any mixing vessel (20), calendering cylinder
(30), extruder,
temporary substrate (32a), final substrate (32b) or adhesive substrate (14)
and/or any other
process component may be heated or cooled. before, during and/or after
mechanically
compacting, mixing and/or, wherein the film (11) is heated before, during
and/or after applying
the film (11) to the final substrate (32b).
Figure 6 shows example embodiments of the invention wherein a process mixture
(9), such as a
dry blend (1) is converted to a paste (2) by wetting (48), e.g. with a wetter
(47), such as a sprayer,
with one or more processing additives, such as background fluid (8), prior to
or during the first
film forming in a film former (38). The background fluid (8) may be mixed with
a dry blend (1)
to form a paste (2) prior to film forming (42) or during film forming (23, 42)
in a film former
(38), which may also act as a mixer (22) and/or a shearer (41) to mix (31)
and/or shear the dry
blend (1) and background fluid (8). Some or all of the processing additives,
such as background
fluid (8), may be removed when the process mixture passes through any of the
nips of the process
or elsewhere in the process, for instance by evaporation, gravity, or
vibration. In one embodiment
the film (11) exiting the film former (38) may be a dry film (11a). In some
embodiments (Figure
6a and 6b) the film exiting the film former (38) may be a pasty film (11b).
The film (11) may
exit the film former as a freestanding film (11). Additional processing
additives, such as
background fluid (8), may be added to the freestanding film (11) to with an
additional wetter,
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such as a sprayer (47), to maintain or regenerate a paste (2) or pasty film (1
lb). The freestanding
or supported pasty film (1 lb) may be fed into another film former (42) /
mixer (22) / shearer (41)
to further process (e.g. mix and/or make thinner) the film (not shown). This
combined wetting
and/or forming and/or mixing and/or shearing process (49) may be repeated any
number of times
(not shown) to control the film thickness and other properties. Alternatively,
as shown in Figure
6c, the film may be applied to a substrate (32), such as an adhesive substrate
(14) and/or a current
collector (17) in a film applier (39). The film applier (39) may further form
the film (42) and act
as a mixer (22) and/or shearer (41). The film (11) exiting the film applier
(39) may be a dry film
(11a) or a pasty film (11b). Additional processing additives, such as
background fluid (8), may
be added to the freestanding and/or supported film (11) with an additional
wetter, such as a
sprayer (47), to maintain or regenerate a paste (2) or pasty film (11 a). The
supported pasty film
(lib) may be fed into another film former (42) / mixer (22) / shearer (41) to
further process (e.g.
mix and/or make thinner) the film. This combined wetting and/or forming and/or
mixing and/or
shearing process (49) may be repeated any number of times, for instance in
series (not shown),
to control the film thickness and other film properties.
Figure 5a shows one embodiment of an electrochemical device (40) according to
the invention.
The electrochemical device (40) may comprise an electrode (12), such as an
anode (12a) and/or
a cathode (12b) and an electrolyte (29). The anode (12a) and cathode (12b) may
comprise a dry
film (11a) and a current collector (17), the anodic current collector (17a) as
part of the anode
(12a) and the cathodic current collector (17b) as part of the cathode (12b).
The electrode (12)
may comprise elements of the process mixture (9), such as the dry blend (1) or
paste (2). The
electrode may comprise elements of an article (10), such as a film (11), such
as a dry film (ha)
or pasty film (11b). The device may comprise an article comprising a dry film
(11a). The
components of the device may be made my any of the previously presented means
or methods.
Figure 5b shows one embodiment of the electrochemical device (40) in which the
device is an
electrochemical cell (33). The electrochemical cell (33) may comprise an anode
(12a) of the
invention, a cathode (12b) of the invention, and an electrolyte (29) between
them. Figure Sc
shows the embodiment of Figure 5b, further comprising a separator (24) between
the anode (12a)
and cathode (12b). In one embodiment of the invention, the dry blend (1)
and/or the dry film
(11a) of the article (10) are adhered to or otherwise coupled with to the
separator (24). The
bonding may be by any means, but dry bonding is preferred. The electrochemical
cell (33) may
be, for instance, a battery cell, a supercapacitor cell or an
electrodeposition cell.
Although certain embodiments and examples are described below, those of skill
in the art will
appreciate that the invention extends beyond the specifically disclosed
embodiments and /or uses
and obvious modifications and equivalents thereof. Thus, it is intended that
the scope of the
invention herein disclosed should not be limited by any particular embodiments
described below.
EXAMPLES
Example 1.
160.0g of dry active material (3a) NaCl and 40.0g of dry matrix material (5)
ketjen black were
mixed (21) in a mixer (22) comprising a ball mill with 4kg of 5mm stainless
steel (SS316) balls
in a mixing vessel (20), a 180mm diameter stainless steel barrel, at 70RPM for
10 hours to
produce a dry active composite (4a). The resulting mixture of dry active
composite (4a) in powder
form was sifted through a 2mm stainless steel mesh to remove the largest
particles. 19.0g of
resulting dry active composite (4a) powder was manually mixed (21) in a mixing
vessel (20) with
1.0g of Daikin F104 PTFE and mixed (21) and sheared (41) in an electric mortar
mixer (22) for
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7 minutes at 130C to fibrillate the binder (6) and form produce flakes of dry
blend (1). Resulting
film was broken into flakes. The dry flakes were further mixed (21) and
sheared (41) using Retch
ZM200 homogenizing machine at 8000RPM using a 12-tooth rotor, and 500 um
sieve. The
resulting dry blend (1) powder was fed into the gap between two calendering
cylinders (30) of a
film former (38) calender machine to produce a dry film (11a), which was also
a freestanding
film (11c), wherein the rollers were pre-heated up to 100C, a linear force of
3000N was applied
and the velocity of each of the calendering cylinders were 10mm/sec and
5mm/sec respectively,
with the gap between two calendering cylinders (30) set to 50 um. Afterwards,
the freestanding
dry film (11a, 11c) was laminated onto an nickel mesh substrate (14, 32) by
feeding the
freestanding dry film (11a, 11c) and the aluminum mesh substrate (14,32) into
the gap between
two calendering cylinders (30) of a film applier (39) calender machine to
produce a cathode (21a),
wherein the calendering cylinders were pre-heated up to 100C, a linear force
of 3000N was
applied and the velocity of each of the calendering cylinders were 5mm/sec and
5mm/sec
respectively and the gap was 150 um. The produced cathode was assembled into
an
electrochemical cell together with a glass fiber seperator and a nickel anode
and NaA1C14:1.5S02
electrolyte.
Example 2.
47.5g of dry active material (3a) NaF and 2.5g of dry matrix material (5) ketj
en black were mixed
(21) in a mixer (22) comprising a ball mill with 4kg of 5mm stainless steel
(SS316) balls in
mixing vessel (20), a 180mm diameter stainless steel barrel, at 70RPM for 10
hours to produce a
dry active composite (4a). The resulting powder of dry active composite (4a)
in powder form was
sifted through a 2mm stainless steel mesh to remove the largest particles.
19.0g of resulting dry
active composite (4a) powder was manually mixed (21) in a mixing vessel (20)
with 1.0g of
Daikin F104 PTFE and mixed (21) and sheared (41) in an electric mortar mixer
(22) for 7 minutes
at 130C to fibrillate the binder (6) and form produce flakes of dry blend (1).
The dry flakes were
further mixed (21) and sheared (41) using Retch ZM200 homogenizing machine at
8000RPM
using a 12-tooth rotor, and 500 p.m sieve. The resulting dry blend (1) powder
was fed into the
gap between two calendering cylinders (30) of a film former (38) calender
machine to produce a
dry film (11a), which was also a freestanding film (11c), wherein the rollers
were pre-heated up
to 100C, a linear force of 3000N was applied and the velocity of each of the
calendering cylinders
were 10mm/sec and 5mm/sec respectively, with the gap between two calendering
cylinders (30)
set to 50 um. Afterwards, the freestanding dry film (11 a, 11 c) was laminated
onto an nickel mesh
substrate (14, 32) by feeding the freestanding dry film (11a, 11c) and the
aluminum mesh
substrate (14,32) into the gap between two calendering cylinders (30) of a
film applier (39)
calender machine to produce a cathode (21a), wherein the calendering cylinders
were pre-heated
up to 100C, a linear force of 3000N was applied and the velocity of each of
the calendering
cylinders were 5mm/sec and 5mm/sec respectively and the gap was 150 um. The
produced
cathode was assembled into an electrochemical cell together with a glass fiber
seperator and a
nickel anode and NaA1C14:1.5S02 electrolyte.
Example 3:
Active material (3a) carbon-coated Lithium Manganese Iron Phosphate (LMFP) and
matrix
material (5) carbon black were mixed (21) in a mixer (22) in the absence of a
dispersant (25) with
weight proportions 93.6:6.38 until visually homogeneous to produce a dry
active composite (4a).
Dry binder (6) PTFE Daikin F104 was then added to the mixture and was mixed
(21) in a mixer
(22) with the resulting mixture in weight proportion 6:94 until visually
homogeneous. The
resulting powder was then mixed (21) in Mortar mixer (22) with pre-heated
mortar and pestle up
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PCT/F12020/050525
to 110C until the powder mixture became plastiline-like. Then, the resulting
plastiline mixture
was then sheared (41) using ultra centrifugal milling machine. The resulting
dry blend (1) powder
was fed into the gap between two calendering cylinders (30) of a film former
(38) calender
machine to produce a dry film (1 la), which was also a freestanding film
(11c), wherein the rollers
were pre-heated up to 100C, a linear force of 8200N was applied and the
velocity of each of the
calendering cylinders were lmm/sec and 3mm/sec respectively. Afterwards, the
freestanding dry
film (11a, 11c) was laminated onto an aluminum mesh substrate (14, 32) by
feeding the
freestanding dry film (11a, 11c) and the aluminum mesh substrate (14,32) into
the gap between
two calendering cylinders (30) of a film applier (39) calender machine to
produce a cathode (21a),
wherein the cylinders (30) were pre-heated up to 100C, a linear force of 8200N
was applied and
the velocity of each of the calendering cylinders were lmm/sec and 5mm/sec
respectively. The
produced cathode was assembled into an electrochemical cell together with a
glass fiber seperator
and a graphite anode and 1 molar LiDFOB electrolyte.
Example 4:
3.0g of active material (3) Na2S03 and 3.0g of matrix material (5) ketj en
black were mixed (21)
in a mixer (22), ball milled with 4 kg of 5mm stainless steel (SS316) balls,
in a mixing vessel
(20), a 180mm diameter stainless steel barrel at 70RPM for 10 hours for form a
dry active
composite (4a). The resulting dry active composite (4a) powder was mixed (21)
in a mixer (22)
with 1.2g of binder (6), stabilized 60% PTFE, suspension in dispersant (25),
water diluted by
7.5g of isopropanol and 7.5g of water, which, in this case was a suspendant
(25a). After
homogenization the resulting material was further mixed (21) and sheared (41)
in an electric
mortar for 10 minutes to fibrillize the binder (6) and produce a paste (2).
This resulting paste (2)
was fed into the gap between two calendering cylinders (30) of a film former
(38) calender
machine to produce a pasty film (lib), which was also a freestanding film
(11c), wherein the
cylinders (30) were at room temperature and the velocity of both of the
calendering cylinders
were 10mm/sec, with the gap between two calendering cylinders (30) set to 150
gm.
Example 5:
Active material mixture (3) comprising NaCl and matrix material (5) ketj en
black were combined
in a ball mill with stainless steel (SS316) balls, in a mixing vessel, a 180mm
diameter stainless
steel barrel, at 70 RPM for 10 hours to form a dry active composite (4a) PTFE
was added to the
same barrel and milled for 1 hour more at the same conditions. The resulting
material was sprayed
with isopropanol to produce a paste having approximately 5% isopropanol by
mass and fed into
the gap between two calendering cylinders of film former calender machine to
produce a thick
free-standing film, wherein the cylinders were at room temperature and the
velocity of both of
the calendering cylinders were 5 mm/s with the gap between two calendering
cylinders set to
1000 gm. Most of the isopropanol was removed from the material by calendering.
The resulting
film thickness then was decreased by subsequently wetting the film by spraying
with isopropanol
to maintain 5% isopropanol by mass and passing the film between the calender
cylinders multiple
times with a subsequent decrease of the gap between passes and comparing
actual film thickness
to target thickness (typical 300 gm) to determine termination of the process.
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RECTIFIED SHEET (RULE 91) ISA/EP
